Ag(I)‐Catalyzed Chlorination of Linezolid during Water Treatment: Kinetics and Mechanism

The kinetic and mechanistic study of Ag(I)‐catalyzed chlorination of linezolid (LNZ) by free available chlorine (FAC) was investigated at environmentally relevant pH 4.0–9.0. Apparent second‐order rate constants decreased with an increase in pH of the reaction mixture. The apparent second‐order rate constant for uncatalyzed reaction, e.g., k″_app = 8.15 dm³ mol⁻¹ s⁻¹ at pH 4.0 and k″_app. = 0.076 dm³ mol⁻¹ s⁻¹ at pH 9.0 and 25 ± 0.2°C and for Ag(I) catalyzed reaction total apparent second‐order rate constant, e.g., k″_app = 51.50 dm³ mol⁻¹ s⁻¹ at pH 4.0 and k″_app. = 1.03 dm³ mol⁻¹ s⁻¹ at pH 9.0 and 25 ± 0.2°C. The Ag(I) catalyst accelerates the reaction of LNZ with FAC by 10‐fold. A mechanism involving electrophilic halogenation has been proposed based on the kinetic data and LC/ESI/MS spectra. The influence of temperature on the rate of reaction was studied; the rate constants were found to increase with an increase in temperature. The thermodynamic activation parameters E_a, ΔH^#, ΔS^#, and ΔG^# were evaluated for the reaction and discussed. The influence of catalyst, initially added product, dielectric constant, and ionic strength on the rate of reaction was also investigated. The monochlorinated substituted product along with degraded one was formed by the reaction of LNZ with FAC.